Semiconductors

1. A polymer, comprising a repeating unit of formula (I):

—[Ar 3 ] c —[Ar 2 ] b —[Ar 1 ] a —Y(R 1 ) n1 (R 2 ) n2 —[Ar 1′ ] a′ , —[Ar 2′ ] b′ , —[Ar 3′ ] c′ —  (I),

wherein

a is 0, 1, 2, or 3;

a′ is 0, 1, 2, or 3;

b is 0, 1, 2, or 3;

b′ is 0, 1, 2, or 3;

c is 0, 1, 2, or 3;

c′ is 0, 1, 2, or 3;

n1 is 1, or 2;

n2 is 1, or 2;

Y is a bivalent heterocyclic group, or ring system, which may optionally be substituted;

Ar 1 , Ar 1′ , Ar 2 , Ar 2′ , Ar 3 and Ar 3′ are independently of each other a C 6 -C 24 arylen group, which can optionally be substituted, or a C 2 -C 20 heteroarylen group, which can optionally be substituted;

R 1 and R 2 in each occurrence are independently of each other hydrogen, C 5 -C 12 cycloalkyl, COR 38 , C 1 -C 50 alkyl, C 3 -C 50 alkenyl, or C 3 -C 50 alkynyl, which can optionally be substituted one or more times with C 1 -C 12 alkoxy, halogen, C 5 -C 8 cycloalkyl, cyano, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or a silyl group; and/or can optionally be further interrupted by one or more —O—, —S—, —NR 39 —, —CONR 39 —, —NR 39 CO—, —COO—, —CO—, or —OCO—, or a group of formula:

i is an integer from 1 to 18;

R 70 , R 71 and R 72 are independently of each other hydrogen, C 1 -C 50 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, C 2 -C 50 alkenyl or C 2 -C 50 alkynyl which can optionally be substituted one or more times with C 1 -C 12 alkoxy, halogen (especially F), C 5 -C 8 cycloalkyl, cyano, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or a silyl group; and/or can optionally be further interrupted by one or more —O—, —S—, —NR 39 —, —CONR 39 —, —NR 39 CO—, —COO—, —CO—, or —OCO—; with the proviso that at least one of the substituents R 70 , R 71 and R 72 is different from hydrogen;

R 38 is C 1 -C 50 alkyl, C 2 -C 50 alkenyl, C 2 -C 50 alkynyl or C 1 -C 50 alkoxy, which can optionally be substituted one or more times with C 1 -C 12 alkoxy, halogen, C 5 -C 8 cycloalkyl, cyano, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or a silyl group; and/or can optionally be further interrupted by one or more —O—, —S—, —NR 39 —, —CONR 39 —, —NR 39 CO—, —COO—, —CO—, or —OCO—; and

R 39 is hydrogen, C 1 -C 25 alkyl, C 1 -C 18 haloalkyl, C 7 -C 25 arylalkyl, or C 1 -C 18 alkanoyl,

with the proviso that at least one of R 1 and R 2 is a group of formula (II).

2. The polymer according to claim 1 , wherein —Y(R 1 ) n1 (R 2 ) n2 — is a group of formula:

which may optionally be substituted,

wherein:

R 1 and R 2 are defined in claim 1 ; and

R 1′ and R 2′ have the meaning of with the proviso that in case —Y(R 1 ) n1 (R 2 ) n2 — is a group of formula:

a and a′ are not 0.

3. The polymer according to claim 1 , wherein Ar 1 and Ar 1′ are independently of each other a group of formula

wherein:

R 3 and R 3′ are independently of each other hydrogen, halogen, halogenated C 1 -C 25 alkyl, especially CF 3 , cyano, C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 4 , R 4′ , R 5 , R 5′ , R 6 and R 6′ are independently of each other hydrogen, halogen, halogenated C 1 -C 25 alkyl, especially CF 3 , cyano, C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 25 arylalkyl,

R 8 and R 8′ are independently of each other hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 25 alkyl, or C 1 -C 25 alkoxy, or C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 arylalkyl,

R 11 and R 11′ are independently of each other C 1 -C 25 alkyl group, especially a C 1 -C 8 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;

R 12 and R 12′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or R 13 ;

R 13 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group;

R 103′ is C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; and

R 114 and R 114′ are independently of each other hydrogen, cyano, COOR 103′ , a C 1 -C 25 alkyl group, or C 6 -C 14 aryl or C 2 -C 20 heteroaryl.

4. The polymer according to claim 3 , wherein:

Ar 2 , Ar 2′ , Ar 3 and Ar 3′ have independently of each other the meaning of Ar 1 ;

Ar 1 is defined in claim 3 , or are independently of each other

R 104 and R 104′ are independently of each other hydrogen, cyano, COOR 103 , a C 1 -C 25 alkyl group, or C 6 -C 14 aryl or C 2 -C 20 heteroaryl;

R 105 , R 105′ , R 106 and R 106′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 107 is hydrogen, C 7 -C 25 arylalkyl, C 6 -C 20 aryl; C 6 -C 20 aryl which is substituted by C 1 -C 25 alkyl, or C 1 -C 25 alkoxy; C 1 -C 18 perfluoroalkyl; C 1 -C 25 alkyl; especially C 3 -C 25 alkyl, which may be interrupted by —O—, or —S—; or —COOR 103 ; wherein R 103 is C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms;

R 108 and R 109 are independently of each other hydrogen, C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 2 arylalkyl;

R 115 and R 115′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, especially C 3 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 2 arylalkyl, or

and

R 116 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group.

5. The polymer according to claim 2 , comprising a repeating unit of formula

wherein:

R 3 and R 3′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, or C 1 -C 25 alkoxy; and

R 1 , R 2 , R 1′ and R 2′ are defined in claim 2 .

6. The polymer according to claim 1 , comprising a repeating unit of formula:

wherein:

R 3 and R 3′ are independently of each other hydrogen, fluorine, C 1 -C 25 alkyl, C 1 -C 25 alkoxy; and

R 1 and R 2 are defined in claim 1 .

7. The polymer according to claim 4 , comprising a repeating unit -[A]-[COM] n3 - (V), wherein:

A is a unit of formula (I);

COM has the meaning of Ar 2 ;

Ar 2 is defined in claim 4 ;

n3 is an integer of 1 to 4; and

COM can be the same or, different in each occurrence.

8. The polymer according to claim 7 , wherein the repeating unit -[A]-[COM] n3 - is a repeating unit of formula:

wherein:

R 3 and R 3′ are independently of each other hydrogen, fluorine, C 1 -C 25 alkyl, or C 1 -C 25 alkoxy; and

R 1 and R 2 are defined in claim 1 .

9. The polymer according to claim 1 , which is a polymer of formula:

wherein:

n is 4 to 1000, and

R 1 and R 2 are defined in claim 1 .

10. The polymer according to claim 1 , wherein:

R 1 , R 2 , R 1′ and R 2′ are a group of formula:

i is an integer from 1 to 10; and

R 70 , R 71 and R 72 are independently of each other hydrogen or C 1 -C 50 alkyl,

with the proviso that at least one of the substituents R 70 , R 71 and R 72 is different from hydrogen.

11. The polymer according to claim 10 , wherein, in the group of formula at least two of the substituents R 70 , R 71 and R 72 are different from hydrogen.

12. The polymer according to claim 10 , wherein:

R 1 , R 2 , R 1′ and R 2′ are a group of formula (II):

i is an integer from 1 to 5; and

R 70 , R 71 and R 72 are independently of each other hydrogen or C 1 -C 36 alkyl,

with the proviso that two of the substituents R 70 , R 71 and R 72 are different from hydrogen.

13. An organic semiconductor material, layer, or component, comprising a polymer according to claim 1 .

14. A semiconductor device, comprising a polymer according to claim 1 .

15. A process for preparing an organic semiconductor device, the process comprising applying a solution and/or dispersion of a polymer according to claim 1 in at least one organic solvent to a substrate and removing the at least one solvent.

16. A device, comprising the polymer of claim 1 , wherein the device is selected from the group consisting of a photovoltaic device, a photodiode and an organic field effect transistor.

17. A compound of formula (X):

X 3 —[Ar 3 ] c —[Ar 2 ] b —[Ar 1 ] a —Y(R 1 ) n1 (R 2 ) n2 —[Ar 1′ ] a′ —[Ar 2′ —[Ar 3′ ] c′ —X 4   (X),

wherein:

a is 0, 1, 2, or 3;

a′ is 0, 1, 2, or 3;

b is 0, 1, 2, or 3;

b′ is 0, 1, 2, or 3;

c is 0, 1, 2, or 3;

c′ is 0, 1, 2, or 3;

n1 is 1, or 2;

n2 is 1, or 2;

Y is a bivalent heterocyclic group, or ring system, which may optionally be substituted;

Ar 1 , Ar 1′ , Ar 2 , Ar 2′ , Ar 3 and Ar 3′ are independently of each other a C 6 -C 24 arylen group, which can optionally be substituted, or a C 2 -C 20 heteroarylen group, which can optionally be substituted;

R 1 and R 2 in each occurrence are independently of each other hydrogen, C 5 -C 12 cycloalkyl, COR 38 , C 1 -C 50 alkyl, C 3 -C 50 alkenyl, or C 3 -C 50 alkynyl, which can optionally be substituted one or more times with C 1 -C 12 alkoxy, halogen, C 5 -C 8 cycloalkyl, cyano, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or a silyl group; and/or can optionally be further interrupted by one or more —O—, —S—, —NR 39 —, —CONR 39 —, —NR 39 CO—, —COO—, —CO—, or —OCO—, or a group of formula:

i is an integer from 1 to 18;

R 70 , R 71 and R 72 are independently of each other hydrogen, C 1 -C 50 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, C 2 -C 50 alkenyl or C 2 -C 50 alkynyl which can optionally be substituted one or more times with C 1 -C 12 alkoxy, halogen (especially F), C 5 -C 8 cycloalkyl, cyano, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or a silyl group; and/or can optionally be further interrupted by one or more —O—, —S—, —NR 39 —, —CONR 39 —, —NR 39 CO—, —COO—, —CO—, or —OCO—; with the proviso that at least one of the substituents R 70 , R 71 and R 72 is different from hydrogen;

R 38 is C 1 -C 50 alkyl, C 2 -C 50 alkenyl, C 2 -C 50 alkynyl or C 1 -C 50 alkoxy, which can optionally be substituted one or more times with C 1 -C 12 alkoxy, halogen, C 5 -C 8 cycloalkyl, cyano, C 6 -C 24 aryl, C 2 -C 20 heteroaryl, or a silyl group; and/or can optionally be further interrupted by one or more —O—, —S—, —NR 39 —, —CONR 39 —, —NR 39 CO—, —COO—, —CO—, or —OCO—; and

R 39 is hydrogen, C 1 -C 25 alkyl, C 1 -C 18 haloalkyl, C 7 -C 25 arylalkyl, or C 1 -C 18 alkanoyl;

X 3 and X 4 are independently of each other hydrogen, halogen, ZnX 12 , —SnR 207 R 208 R 209 ;

R 207 , R 208 and R 209 are identical or different and are H or C 1 -C 6 alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X 12 is a halogen atom; or —OS(O) 2 CF 3 , —OS(O) 2 -aryl, —OS(O) 2 CH 3 , —B(OH) 2 , —B(OY 1 ) 2 ,

—BF 4 Na, or —BF 4 K;

Y 1 is independently in each occurrence a C 1 -C 10 alkyl group;

Y 2 is independently in each occurrence an optionally substituted C 2 -C 10 alkylene group; and

Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 10 alkyl group.